Lignocellulose method and reaction product



United States Patent 3,208,864 LIGNOCELLULOSE METHOD AND REACTION PRODUCT William T. Glab, Dubuque, Iowa, assignor to Caradco Incorporated, a corporation of Iowa No Drawing. Original application Oct. 22, 1958, Ser. No. 768,832, now Patent No. 3,033,695, dated May 8, 1962. Divided and this application May 4, 1962, Ser. No. 192,361

This invention relates to methods of making a lignocellulose product and to the products resulting therefrom.

This application is a division of my co-pending application Serial No. 768,832, filed October 22, 1958, now Patent No. 3,033,695, which was a continuation-in-part of application Serial No. 764,232, filed September 30, 1958, now Patent No. 2,984,578.

It is an object of this invention to provide an improved method of making a moldable composition comprising reacting an essentially dry mixture including comminuted lignocelluloe and a reactant of the class consisting of inorganic sulfates, inorganic sulfites, inorganic bisulfites and inorganic sulfides, organic alcohols and polyols, organic aldehydes and ketones, nitrogen compounds and organic unsaturated compounds.

Another object of this invention is to provide such a method wherein the amount of reactant is about 0.30% by weight of the lignocellulose and the reaction is conducted in an atmosphere of moisture vapor such as steam at about 275475 F. at a pressure of about 50-550 pounds per square inch gauge, and for about 4-60 minutes.

A further object of the invention is to provide lignocellulose products prepared by the above methods.

Other objects and advantages of the invention will be given herein and will be apparent from the following description of several embodiments of the invention.

An important advantage of the invention appears to be the controlling of the reaction so that the alpha cellulose is reduced in molecular size sufficiently to prevent substantial swelling of subsequently fabricated products but not to the extent that toughness of fiber is lost. The latter occurs under drastic degradation and starts to become quite serious when approximately 25% of the lignocellulose has been lost as either gaseous or soluble byproducts.

Another advantage appears to be the plasticization of the lignin component during the controlled cellulose degradation so that the lignin can subsequently be made to flow and function as a binder between the comminuted lignocellulose particles.

Another advantage is the provision of a relatively dry system so that high capacity for the process of, for ex ample, wood waste is attained. This is not possible in a wet process such as ordinarily found in a pulping process in which the reactor is charged with approximately 90% water which takes up space as well as requires the addition of large amounts of energy to bring the reaction medium to the proper temperature.

Another advantage is the contacting of lignocellulose or dry mixes of lignocellulose and other ingredients under superatmospheric pressure with a vapor or combination of vapors functioning both as a heat transfer medium and as a reactant.

In the method of this invention an essentially dry mixture including comminuted lignocellulose and a reactant is reacted as by heating while confining the lignocellulose and the reactant under superatmospheric pressure as in an autoclave. During the reaction the lignocelulose bond is apparently broken and the lignin is released to operate as a binder.

It appears that the hemi-celluloses are the primary con ice stituents of the lignocellulose which are attacked by bydrolysis, but that under the high pressure and temperature of this invention a portion of the hydrolysates are further converted to higher molecular weight materials which can function as plasticizers for the autoclave product when it is molded. At the same time, a controlled degradation of the alpha cellulose is carried out to the extent that the desired degree of moisture stability is obtained in the molded or extruded products without an unnecessary loss of toughness. These actions are believed to occur, although they have not been absolutely proven.

The methods of this invention may be carried out batchwise in an autoclave or a sealed press or continuously in a continuous contactor.

The lignocellulose which appears dry to the touch actually contains up to about 30% water before the reaction begins.

The lignocellulose which may be used in this invention includes wood as well as other lignocellulosic vegetable materials. The lignocellulose is finely divided so that the particles are preferably not more than 20 mesh in size as measured by a standard screen although smaller sizes are preferred.

During the reaction which takes place in a confined atmosphere under superatmospheric pressure various reaction products are produced, although the exact nature of the reaction is not understood. It appears that the reaction products are either inert so that the product itself is inert, have a binding action such as is true of the lignin produced, are gaseous by-products, or are polymerized. By hydrolyzing and partially removing, or polymerizing the hemi-celluloses to lignin type materials, the ratio of lignin and other binders to the alpha cellulose is increased so that the general nature of the lignocellulose mixture is drastically changed.

The high pressure method of this invention has a number of advantages that are not possible with reactions taking place at ordinary pressure and in an unconfined state. In the preferred process, steam is introduced into the autoclave both for heating purposes and to supply moisture for the reaction. In the high pressure method of this invention heat transfer is much more rapid so that in general a shorter reaction time is required. Furthermore, energy losses during the reaction are greatly reduced. In the ordinary reacting mixture these energy losses result from the release of volatile materials such as water vapor, gaseous reaction by-products and the like. As the reaction here takes place in a confined atmosphere, no such losses occur to any material degree. Furthermore, the energy supplied by the steam or vapor is utilized to heat only the lignocellulose with its approximately normal moisture content in contrast to pulping type reactions where large quantities of water are present, requiring far greater expenditures of energy.

Another important advantage of this process is the close control that is obtained over the reaction. Thus, the temperature of the reacting mass, and hence the rate of reaction, can be easily raised or lowered by controlling the rate of flow, pressure and the temperature of the heat transfer medium which may be steam, oil vapor, or other high temperature fluids. Reactions may easily be stopped by flashing the heat transfer medium from the autoclave, since the large energy loss on expansion cools the reacting mass below the incipient reaction point. During the practice of the process the reacting mixture may be confined in a jacketed vessel with the heating medium introduced to the chambers in the quantity and temperature desired.

A very important advantage of the invention is that volatile reactants may be used as the reacting mass is in a confined space. Volatile reactants are impossible,

of course, when the reacting mass is in the open. As a result of the rapid heat transfer achieved by this invention and the penetration of volatile reactants, the reaction not only proceeds to completion in a much shorter time but the final product tends to be more uniform than where the reactants are heated such as in an ordinary process that depends upon surface temperature differentials.

Tests have shown that the confining of the reacting mass in the autoclave not only causes retention of the by-products of reaction within the mass even when the by-products are gaseous but also causes polymerization of all or a portion of these by-products, even some that are gaseous. In so-called wet processes, large quantities of the by-products of reaction go into solution and are lost.

Another advantage of the invention is that the volatile by-products are easily collected and removed at low cost for later use where desired or to prevent the creation of a nuisance.

Where volatile reactants are used no mechanical mix ing of the ingredients is required. This results in a considerable saving in time, labor and other factors. Thus, in these instances, it is only necessary to charge the reactor with the lignocellulose and introduce the volatile materials into the reactor under superatmospheric pres sure. In addition, if desired, the reactants can be changed or modified during the course of a run. This is not possible to such a degree in a wet process where the charge generally contains less than 50% of lignocellulose, and addition of reactants would in many cases cause prohibitive amountsto go into solution.

A further advantage of utilizing the vapor process is that the volatile content of the reaction product which is primarily moisture can be controlled. By using superheated steam with a sufiicient degree of superheat, products on the order of 1% or lower volatile content can be obtained. Under normal conditions, to degrees of superheat at 300 pounds per square inch steam pressure will produce a product of 35% volatile content. Thus, the expensive drying step connected with wet processes can be avoided.

Because of rapid penetration of reactants under high pressure, larger sized particles can be charged to the autoclave than would ordinarily be used, and a savings in size reduction cost made as a result of lower power re quirements to reduce the treated material in comparison with raw lignocellulose.

In addition, where flat stock of preformed material is being made as in a sealed press, the products can be made much thicker and more uniform than in an ordinary press which depends upon high platen temperature for heat transfer, and in many cases requires almost prohibitive cycle time.

The reactant is thoroughly. mixed with the finely divided lignocellulose and then heated at a temperature and pressure and for a time suflicient to react at least a portion and preferably a major portion of the reactant or reactants with the lignocellulose.

In the preferred process the temperature of the steam is between about 275-475 F. and the pressure is between about 50-550 pounds per square inch gauge. The amount of reactant is preferably between about 0.1-30.0% by weight of the lignocellulose.

In the practice of this invention where solid reactants are used, they are preferably finely divided, and blended with the lignocellulose such as in a mixer, prior to the reaction in the autoclave. When soluble, they are preferably added in the form of solutions. When liquids are used, they may be diluted with water or other solvents so that they will be thoroughly. dispersed throughout the mass of lignocellulose. Preferably an amount of solu- Table I Autoclave Reac- Ex. Reactant tion Time, Temp., Press, Min. F. p.s.i.

2% Ammonium Sulfate. 20 440 300 2% Calcium Su1fate+5% Vrnsol-- 20 440 300 1% Zinc Sulfate-.- 25 400 200 2% Zinc Su1fate 20 440 300 2% Ferrous Sulfa 20 400 200 2% Ferrous Sulfate- 20 440 300 2% Ferric Sulfate 20 440 300 1% Ferric Sulfate+5% Vinsol 20 440 300 1% Cupric Sulfate 20 400 200 10 440 300 20 440 300 2% Aluminum Sulfate" 20 440 300 13---- 1% lAluminum Sulfate+5% "Vin- 20 400 300 so 14.--- 2% 1Aluminum Sulfate+5% Vin- 20 440 300 so 15..-- 1% Aluminum Sulfate+5% Lignin 20 400 200 16 1% Aluminum Sulfate+5% Phenol 20 400 200 Residue.

17.--. 2% Sodium Sulfite 25 440 300 18 2% Sodium Sulfite+6% Sulfur 25 440 300 19 30 460 400 30 460 400 20 440 300 30 460 400 20 440 300 20 440 300 10% Phthalic Anhydride 20 440 300 26.--- 5% Phthalie Anhydride+1% Ferric 20 400 200 Chloride. 27---- 10% Tall Oil 20 440 300 28 5% Tall Oil 30 460 400 29.--- 5'7 Tall Oi1+5% Calcium Chloride 20 440 300 30---- 5 9 Tall Oil+5% Vinsol+3% Cal- 20 440 300 ciurn Chloride. 31--.- 5% Tall Oil+1% Zinc Chloride 15 440 300 32"-- 5% Tall Oil+1% Ferric Chloride 20 400 200 33-.-- 10%d1all Oil+1% Aluminum Chlo- 5 400 200 r1 e. 34.--- 10%dTal1 Oil+1% Aluminum Chlo- 20 440 300 n e. 35---- 10%d1all Oil+2% Aluminum Chloso s25 50 ri e. 36--.- 10% Tall Oil+1% Acetyl Chloride-" 10 375 150 37 10% Tall Oil+10% Sulfur 20 440 300 38 5% Linseed Oil 30 440 300 39 10% Linseed Oil 30 460 400 40.--- 5% Linseed Oil+1% Ferric Chloride. 25 440 300 41 10% Linseed Oil+10% Sulfur.. 20 440 300 42.-" 10% Paraflin Oil+1% Ammonium 20 440 300 Chloride. 43..-- 10% Paraffin Oil+0.5% Aluminum 20 440 300 Chloride.

tion up to about 20% of the weight of the lignocellulose 1 solid is preferably blended with the lignocellulose before the addition of the liquid.

In each of the following examples as set out in Table I, 500 grams of 20 mesh, hammer-milled Ponderosa pine containing only its normal moisture content of approximately 6% was used. To this was added the reactant in the amount specified. In each instance the mixture was ball-milled for about /2 hour to obtain a uniform dispersion of the reactant throughout the mass. The composition was then placed in a heated autoclave and steam was admitted until the pressure and temperature were those specified. The autoclave was held under these conditions for the time specified and then the steam was rapidly flashed oif. During the course of the run, the stated pressure was maintained by venting oif the excess pressure caused by volatile reaction by-products. The granular reaction product which had been cooled below the incipient reaction point by the rapid vapor flash-off was removed from the autoclave, and all particles which had consolidated were thoroughly broken up.

The following Table I lists a number of representative reactions utilizing inorganic sulfates, sulfites, bisulfites and sulfides, unsaturated organic compounds, organic nitrogen compounds, organic alcohols and polyols, and aldehydes and ketones with lignocellulose.

All of the percentages given herein are by weight of the lignocellulose.

Where non-drying types of oils such as paraffin oil and B.R.V. are used, it is believed that they function to limit to some extent the hydrolytic degradation of the alpha cellulose. The reaction products made with oils 5 appear to be less brittle than when plain lignocellulose is reacted with steam.

The organic oils which may be used as reactants herein are those oils which are unsaturated or which contain a functional group that is capable of reacting with the lignocellulose or with lignocellulose products produced under the high pressure-high temperature conditions of this invention. The natural resins and materials set out herein are intended to include naturally occurring reactants of which rosin, Vinsol, turpentine and the like are examples. In fact, the preferred members of this group are materials produced from pine tree products. Vinsol is identified in my prior Patent No. 2,872,330.

In addition to the organic oils, reaction products can be made with lignocellulose and organic alcohols and polyols, aldehydes and ketones, organic nitrogen compounds and organic unsaturated compounds.

Autoclave Reac- Ex. Reactant tion Time, Temp, Press, Min. F. p.s.i.

25% Ethyl Alcohol+50 p.s.i. Sulfur 10 428 140 Dioxide. 10% Isopropyl Alcohol 25 440 300 10% Isopropyl Alcohol+0.5% Alu- 20 440 300 minum Chloride. 10% Isopropyl Alcohol+l% Suliur 20 440 300 10% Allyl Alcohol-{40% Sulfur 20 440 300 10% Ethylene Glycol 30 460 400 10% Ethylene Glycol+l%Alumi- 20 400 200 num Chloride. 20% Ethylene G1ycol+1% Alumi- 20 400 200 num Chloride. 10% Glycerlne+0.5% Aluminum 20 400 200 Chloride. 10% Acetaldehyde 30 440 300 10% Acetaldehyde 30 460 400 10% Acetaldehyde+10% Sulfur: 20 440 300 10% Furfural 25 440 300 10% Furfural+l0% Sulfur 13 440 300 5% Acetone+5p.s.i. Sulfur Dioxide... 20 440 300 Mesityl Oxide-+12% Sulfur 25 440 300 +15% Vinsol. 10% Acetone 30 460 400 10% Butyraldehydc+l2% Sulfur 25 440 300 +15% VinsOl. 10% Acetaldehyde+l2% Sulfur 25 440 300 +15% Vinsol. 5% Glutaraldehyde+l2% Sulfur 25 440 300 +15% inso 5% Aniline 30 440 300 3% Aniline 30 460 400 5% Aniline+l0% Sullur 440 300 3% Triethanolamine 440 300 3% Morpholine 460 400 2% Tetraethanol Ammonium Hy- 30 440 300 droxide. 2% Tetraethanol Ammonium Hy- 30 460 400 droxide. 3% Formamide 30 440 300 3% Formamide. 30 460 400 5% Dicyandiamid 25 440 300 10% Dicyandiamid 20 440 300 5% Melamine 30 440 300 5% Urea+l% Aluminum 0 10 400 200 5% Urea+5p.s.i. Sulfur Dioxide 25 440 300 5% Urea+5% Formaldehyde. 30 460 400 10% Styrene Monomer 30 460 400 10% Styrene Monomer+3% Calcium 20 440 300 Chloride. 10% Styrene l\lonomer+1% Ferric 20 440 300 Chloride. 10% Styrene Monomer+0.5% Alu- 15 440 300 minurn Chloride. 10% Styrene Monomer+1.0% Alu- 20 400 200 ominum Chloride. 10% Styrene Monomer+l0% Suliur 20 440 300 10% Vinyl Acetate Monomer 30 460 400 10g, 1\f inyl Acetate Monomer+l0% 20 440 300 u ur. 10% Dieyclopentadiene 30 460 400 5% Dicyclopentadiene+3% Calcium 20 440 300 Chloride. 5% Dicyclopentadiene+1% Ferric 15 440 300 Chloride. 10% Dicyclopentadiene+l% A111- 10 400 200 minum Chloride. 20% Dicyclopentadiene+10% Sulfur- 25 440 300 The preferred ranges in which the various classes of reactants are used are as follows.

6 Table II Reactant: Preferred amount, percent Inorganic sulfates, sulfites, bisulfites and sulfides 1-15 Alcohols and polyols 2-25 Organic aldehydes and ketones 2-20 Organic nitrogen compounds 0.520 Unsaturated organic compounds 2-25 From the examples cited, it is apparent that a large number of different lignocellulose reactions can be carried out with the methods of this invention to produce materials having a wide variety of properties. Thus, it is possible to produce reaction products which when molded or pressed 'or otherwise formed into products such as boards will possess an optimum of certain desired physical properties such as low water absorption, high strength, relatively high plasticity, or other required properties.

The materials are thus formable at a relatively low temperature in the approximate range of 275375 F. without the use of excessive pressures. The temperature at which the products are formed is not critical since boards can easilybe made at about 400 F. or higher if desired. The ability to form products at lower temperatures is an important property since many of the synthetic thermoplastic resins formable at this temperature can thus be blended with the modified lignocellulose, if it is desired to further vary the physical properties of the product.

Formed products can be produced over a wide density range such as with a specific gravity of from approximately 0.5-1.5 depending upon the temperature and pressure used. The pressure utilized can vary from about 25-5000 p.s.i. depending upon the molding temperature and the final product density desired. In general, the lower pressures are used at the higher temperatures. Where boards or preforms are produced, the pressure is generally between about 25-800 p.s.i., and the temperature between about 300-400 F. If the materials are molded the higher pressures are used and the temperature preferably between about 275-475 F.

Where boards or preforms are made, the particle size of the composition of this invention is preferably between inch-J00 mesh as measured on standard screens. The especially preferred particle size is between 20-50 mesh. The press time is only suflicient to cause the particles to coalesce and bond to each other and to reach the desired board density. The time will, of course, vary with the applied pressure, press temperature and with the material used as well as the thickness of the board. In general, the press time is between about 02-20 minutes. A inch thick board can ordinarily be made in 68 minutes at a temperature of 350 F. and under p.s.i. pressure.

Where the reaction products of this invention are molded, the product is preferably removed from the reaction vessel and then ground to a powder that is preferably not over about 50 mesh in size. The finely divided moldable material is heated to a temperature just sufiicient to flow and fill the mold under the pressure used. The molding time is only sufficient to cause the moldable material to fill the mold and set, and will vary depending upon the type of mold being used, the temperature, the nature of the moldable material and similar factors. In general, the molding time will vary between about 02-15 minutes.

Having described my invention as related to the embodiments set out herein, it is my intention that the invention be not limited by any of the details of description unless otherwise specified but rather be construed broadly Within its spirit and scope as set out in the accompanying claims.

I claim:

1. The method of making a lignocellulose product capable of being pressure molded, consisting essentially of: intimately mixing finely divided lignocellulose that is dry to the touch with about 0.1-30.0% by Weight of a reactant of the class consisting of aniline, triethanolarnine, morpholine, tetraethanol ammonium hydroxide, formamide, dicyandiamide, melamine, urea plus aluminum chloride, urea plus sulfur dioxide and urea plus formaldehydeto provide an essentially dry mixture; heating said dry mixture in a confined atmosphere at an internal pressure of about 50-550 pounds per square inch gauge and a temperature of about 275-475 F. for about 4-60 minutes to react said reactant and lignocellulose; and supplying steam to said confined atmosphere during the reacting to provide heat and a controlled amount 'of moisture to said reaction.

2. A lignocellulose product prepared by the method of claim 1.

'8 References Cited by the Examiner UNITED STATES PATENTS 9/38 Sherrard et a1. 2609 7/42 Hatch 2609 10/42 Loughborough et a1. 264330 5/48 Van der Pyl 106163 12/58 Glab 106-163 2/59 Glab 106--163 12/60 Snyder 106163 FOREIGN PATENTS 12/38 Great Britain.

MORRIS LIEBMAN, Primary Examiner.

LESLIE H. GASTON, Examiner. 

1. THE METHOD OF MAKING A LIGNOCELLULOSE PRODUCT CAPABLE OF BEING PRESSURE MOLDED, CONSISTING ESSENTIALLY OF: INTIMATELY MIXING FINELY DIVIDED LIGNOCELLULOSE THAT IS DRY TO THE TOUCH WITH ABOUT 0.1-30.0% BY WEIGHT OF A REACTANT OF THE CLASS CONSISTING OF ANILINE, TRIETHANOLAMINE, MORPHOLINE, TETRATHANOL AMMINOUM HYDROXIDE, FORMAMIDE, DICYANDIAMIDE, MELAMINE, UREA PLUS ALUMINUM CHLORIDE, UREA PLUS SULFUR DIOXIDE AND UREA PLUS FORMALDEHYDE TO PROVIDE AN ESSENTIALLY DRY MIXTURE; HEATING SAID DRY MIXTURE IN A CONFINED ATMOSPHERE AT AN INTERNAL PRESSURE OF ABOUT 50-550 POUNDS PER SQUARE INCH GAUGE AND A TEMPERATURE OF ABOUT 275-475*F. FOR ABOUT 4-60 MINUTES TO REACT SAID REACTANT AND LIGNOCELLULOSE; AND SUPPLYING STEAM TO SAID CONFINED ATMOSPHERE DURING THE REACTING TO PROVIDE HEAT AND A CONTROLLED AMOUNT OF MOSITURE TO SAID REACTION. 